Du X, Du Y, George S M
Department of Chemical and Biological Engineering, University of Colorado, Boulder, Colorado 80309, USA.
J Phys Chem A. 2008 Oct 2;112(39):9211-9. doi: 10.1021/jp800518v. Epub 2008 Aug 16.
Ultrathin tin oxide films were deposited on SiO2 nanoparticles using atomic layer deposition (ALD) techniques with SnCl4 and H2O2 as the reactants. These SnO(x) films were then exposed to O2 and CO gas pressure at 300 degrees C to measure and understand their ability to serve as CO gas sensors. In situ transmission Fourier transform infrared (FTIR) spectroscopy was used to monitor both the charge conduction in the SnO(x) films and the gas-phase species. The background infrared absorbance measured the electrical conductivity of the SnO(x) films based on Drude-Zener theory. O2 pressure was observed to decrease the SnO(x) film conductivity. Addition of CO pressure then increased the SnO(x) film conductivity. Static experiments also monitored the buildup of gas-phase CO2 reaction products as the CO reacted with oxygen species. These results were consistent with both ionosorption and oxygen-vacancy models for chemiresistant semiconductor gas sensors. Additional experiments demonstrated that O2 pressure was not necessary for the SnO(x) films to detect CO pressure. The background infrared absorbance increased with CO pressure in the absence of O2 pressure. These results indicate that CO can produce oxygen vacancies on the SnO(x) surface that ionize and release electrons that increase the SnO(x) film conductivity, as suggested by the oxygen-vacancy model. The time scale of the response of the SnO(x) films to O2 and CO pressure was also measured by using transient experiments. The ultrathin SnO(x) ALD films with a thickness of approximately 10 A were able to respond to O2 within approximately 100 s and to CO within approximately 10 s. These in situ transmission FTIR spectroscopy help confirm the mechanisms for chemiresistant semiconductor gas sensors.
采用原子层沉积(ALD)技术,以四氯化锡和过氧化氢作为反应物,在二氧化硅纳米颗粒上沉积超薄氧化锡薄膜。然后将这些SnO(x)薄膜在300℃下暴露于氧气和一氧化碳气体压力下,以测量并了解它们作为一氧化碳气体传感器的性能。利用原位透射傅里叶变换红外(FTIR)光谱来监测SnO(x)薄膜中的电荷传导以及气相物种。基于德鲁德-齐纳理论,背景红外吸光度测量了SnO(x)薄膜的电导率。观察到氧气压力会降低SnO(x)薄膜的电导率。随后添加一氧化碳压力则会增加SnO(x)薄膜的电导率。静态实验还监测了一氧化碳与氧物种反应时气相二氧化碳反应产物的积累情况。这些结果与耐化学半导体气体传感器的离子吸附和氧空位模型均相符。额外的实验表明,对于SnO(x)薄膜检测一氧化碳压力而言,氧气压力并非必需。在没有氧气压力的情况下,背景红外吸光度随一氧化碳压力增加。这些结果表明,正如氧空位模型所暗示的那样,一氧化碳能够在SnO(x)表面产生氧空位,这些氧空位会电离并释放电子,从而增加SnO(x)薄膜的电导率。还通过瞬态实验测量了SnO(x)薄膜对氧气和一氧化碳压力响应的时间尺度。厚度约为10埃的超薄SnO(x) ALD薄膜能够在约100秒内对氧气做出响应,并在约10秒内对一氧化碳做出响应。这些原位透射FTIR光谱有助于证实耐化学半导体气体传感器的作用机制。